Electronically Driven Stereogenesis

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The Organic Dynamics Program will support Professor William J. le Noble's study of "Electronically Driven Stereogenesis" in the Chemistry Department at the State University of New York at Stony Brook. He will explore the principle that bond formation at trigonal carbon and bond cleavage at tetragonal carbon are favored in face selectivity on that side which has the most electron-rich sigma bond in the antiperiplanar position. In this project, Professor le Noble is pursuing three major areas of research that will exploit unique advantages of 2,5-disubstituted adamantanes as probes to study stereoelectronic effects in diastereofacial selection. One area of study will involve examination of the scope of a simple rule according to which bond formation (addition reactions: electrophilic addition, nucleophilic addition, pericyclic reactions, etc.) at trigonal carbon and bond cleavage (decarboxylation, fragmentation, solvolysis, etc.) at tetragonal carbon occur at that face which has the most electron rich bond antiperiplanar. The rigidity of the adamantane skeleton guarantees that no rotational motion will shroud the observed face selection in conformational uncertainty. Another area of study deals with the transfer of chirality, and the third area deals with the kinetic studies of solvolysis of 2- and 5-tosyl adamantanes.